Triazine monoazo-dyestuffs



United States Fatent TRIAZINE MONOAZO-DYESTUFFS Henri Riat, Arlesheim,Switzerland, assignor to Ciba Limited, Basel, Switzerland, a Swiss firmNo Drawing. Application September 3, 1957 Serial No. 681,455

Claims priority, application Switzerland September 6, 1956 9 Claims.(Cl. 260-153) This invention provides azo-dyestuffs, which like, forexample, the monoaZo-dyestufi of the formula correspond to the generalformula 2 R1N:NR2-X-R3 in which R represents an aromatic, advantageouslybicyclic, radical of a diazo-component which contains at least as manysulfonic acid groups as 6-rnembered aromatic rings and which may containan azo linkage, R represents a benzene radical which is bound in the 4-position to X and in the 1-position to the azo linkage, and whichcontains in the 2-position an acylamino group, X represents a bridgemember bound through a nitrogen atom to R and R represents the radicalof a dihalogentriazine.

The new dyestuffs. of the Formula 2 are made by condensing anamino-azo-dyestuli of the formula in which R and R have the meaningsgiven above, and Y represents an acylatable amino group, with atrihalogen-triazine, especially cyanuiic chloride(2:4:6-trichloro-1z3z5-triazine) in such manner that a primarycondensation product is obtained which contains two exchangeable halogenatoms in the triazine nucleus.

The amino-azo-dyestuifs of the Formula 3 can be made by coupling a1-amino-3-acylaminobenzene with a diazotized aromatic amino-sulfonicacid which contains at least as many sulfonic acid groups as 6-memberedaromatic rings.

Accordingly, in order to prepare an amino-azo-dyestuii of the Formula 3there is used a diazo-component, for example, of the benzene ornaphthalene series, which may contain an azo linkage and which containsat least one sulfonic acid group per 6-membered aromatic ring and maycontain further substitutents, for example, a halogen atom such aschlorine, or a methoxy or ethoxy group. By virtue of the ease with whichthey can be obtained and the good results obtained therewith there areused more especially monoor di-sulfonic acids of aminobenzene forexample, 1-an1inobenzene-2-, -3- or -4-sul-' fonic acid,3-amino-2-hydroxybenzoic acid-S-sulfonic acid, 5-amino-2-hydroxybenzoicacid-3-sulfonic acid, 2- aminobenzoic acid-4- or -5-sulfonic acid orl-aminobenzene-2z5-disulfonic acid, disulfonic acids of amino-azo-Patented Sept. 8, 1959 ice S aC H038 N S0311 obtained by thermalrearrangement of the acid sulfate of the monosulfonic acid obtained bysulfonating 2-(4'- aminophenyl)-6methyl-benzimidazole with concentratedsulfuric acid, and especially ocor ,B-naphthylamine disulfonic acidssuch as l-aminonaphthalene-S:6-disulfonic acid or2-aminonaphthalene-3:6-, -5:7-, -4:8- or -6:8- disulfonic acid.

There are used for coupling with the aforesaid diazocomponent containingsulfonic acid groups 1-amino-3- acylaminobenzenes. The latter maycontain, especially in the 6-position, further substituents, forexample, a lower alkyl or alkoxy group such as a methyl, ethyl, methoxyor ethoxy group. The acyl amino group in the 3-position may be derivedfrom an alkane sulfonic acid or advantageously from a carboxylic acid,and especially an aliphatic carboxylic acid of low molecular weight. Assuch acylamino groups there may be mentioned, for example, theformylamino, acetylarnino, propionylamino, hydroxyacetylamino,hydroxypropionylamino or group. Thus, for example, there areadvantageously used 1-amino-3-acylaminobenzenes of the formula z-o Ol\TH in which Y represents a hydrogen atom or a lower alkyl or loweralkoxy group, and Z represents the methyl, ethyl or hydroxymethyl group,or a lower alkoxy group or a free amino group. As examplesof1-amino-3-acylaminobenzenes of the Formula 4 there may be mentioned:

These l-amino-3-acetylaminobenzenes may be coupled with the aforesaiddiazo-components containing sulfonic acid groups by methods inthemselves known, advantageously in a weakly acid to neutral, forexample, acetic acid, medium.

The condensation of the dyestuiis of the Formula 2 with thetrihalogen-triazines, such as cyanuric chloride, is advantageouslycarried out in the process of this invention in the presence of anacid-binding agent such as sodium acetate or sodium carbonate, and thecondensation is conducted in such manner that the condensation productobtained contains two of the three exchangeable halogen atoms of thetrihalogen-triazine used, for example, by reacting 1 molecularproportion of an amino-azodyestuff of the Formula 2 with at least onemolecular proportion of cyanuric chloride in a weakly acid, neutral toweakly alkaline medium and/ or at a sutficiently low temperature.

Notwithstanding that they contain labile halogen atoms the dyestuffsobtained by the process of this invention can be isolated from themedium in which they are formed, for example, by salting out andfiltration, and worked up into useful dry dyestutl preparations. Theisolation is advantageously carried out at as low a temperature aspossible by salting out and filtration. The dyestuff filtered oil may bedried, if desired after the addition of a neutral or very weaklyalkaline extender. advantageously carried out at not too high atemperature and, if desired, under reduced pressure. In certain cases*dry preparations can be obtained by spray drying the Lrnixture in whichthe dyestutf has been formed, that is to say, without first isolatingthe dyestufl.

By the process of this invention there are obtained valuable newazo-dyestutls which correspond to the Formula 2 and preferably containat least two groups imparting solubility in water.

The new dyestuffs are suitable for dyeing or printing a very widevariety of materials, especially cellulosecontaining materials offibrous structure such as linen, regenerated cellulose and above allcotton and also synthetic artificial fibers of viscose. They areespecially The drying is suitable for dyeing by the process in which thedyestuif is applied at room temperature or at a moderately raisedtemperature to the material to be dyed by the direct dyeing method or bya printing or so-called pad dyeing process from an aqueous bath whichcontains a high saltconcentration and may be alkaline, and the dyestuifis metal may be carried out by methods in themselves"- known. In manycases very valuable dyeings are obtained by working according to theprocess in which a dyeing produced with the metal-free dyestutt' isaftertreated with an aqueous solution which contains a watersoluble, andadvantageously complex, copper compound and a basic condensation productof formaldehyde with a compound containing at least once the atomicgrouping or a compound, such as cyanamide, which is easily convertibleinto a compound containing the aforesaid atomic grouping.

The dyeings produced on cellulose-containing fibers with the newdyestuifs are usually distinguished by the purity of their tints and bytheir good fastness to light and especially by their excellent fastnessto washing.

The following examples illustrate the invention, the parts andpercentages being by weight:

Example 1 30.3 parts of 2-aminonaphthalene-4:8-disulfonic acid arediazotized in the usual manner with 6.9 parts of sodium nitrite in thepresence of hydrochloric acid, and the diazo-compound is coupled with anaqueous solution containing 15 parts of l-amino-3-acetylaminobenzene.There are then slowly added parts of sodium acetate and the whole 'isstirred for four hours at 5l0 C. The amino-monoazo-dyestuif formed issalted out, filtered oil, and dissolved in about 3000 parts of water andthe solution so obtained is neutralized. The solution is run into anaqueous ice-cold suspension of 18.5 parts of cyanuric chloride andstirred for one hour at 05 C. parts of a ZN-aqueous solution of sodiumcarbonate are then added dropwise in such manner that the reactionsolution has a weakly acid reaction (a pH value of 5.5 to 6.5). Whenfree amino groups can no longer be detected, the pH value is adjusted to7.5 to 8 by adding a small amount of sodium carbonate. The dyestutl isthen salted out, filtered off, and dried at 40 C. It dissolves in waterwith a yellow coloration and dyes cotton from an alkaline bath in thepresence of an electrolyte pure reddish yellow tints. The dyeings areremarkably fast to light and washing.

Similar dyestuffs are obtainedby the method described above by using,instead of the aforesaid 2-aminonaphthalone-4:8-disulfonic acid, thecompounds given in column I of the following table and the couplingcomponents given in column II, the tints of the dyeings produced withthe dyestutfs being given in column III:

I II III 1 2-aminonaphthalene-4z8- 3-aminopheny1-urea. reddishdisulfonic acid. yellow. 2 do 1-amino-3- (hydroxyacc- Do.

tylamino) -b enzcnc. 3 do 1 amino 3 propionyl Do.

amiuobenzene. 4 do 1-amino-3-aeetylaminoyellowish G-methoxybenzene.orange. 5. 1-aminonaphthalene-3 :6- Iamin0-3 -aectylami.noreddishdisulfonic acid. benzene. yellow. 6 d0 I-amino-3-acetylamino- Do.

o-methylbenzenc. 7- l-aminobenzene-Zzfi-di- 1-amino-3-acetylaminoyellow.

sulfonic acid. benzene. 8. 1-aminobenzene-3-suldo Do.

ionic acid. 9- 2-arninonaphtha1ene-5:7- l-amino-K-acetylaminoreddishdisulfonic acid. benzene. yellow. 10. 2 (4 aminopheuyl) 6 do yellowmethylbenzthiazole orange. disulfonic acid. 11 4-amin0-1:1-azobenzene-1-amino-3-aeetylaminoyellowish 3:4- disulfonic acid. benzene. orange.12. 2-aminonaphthalene-4:8- 1 amino 3 methane reddish disulfonic acid.sulfonylamino-bcnyellow.

zene.

Example 2 2 parts of the dyestutl obtained as described in the firstparagraph of Example 1 are dissolved in 2000 parts of cold Water. 100parts of well wetted cotton yarn are entered into the resulting dyebathat 2030 C., 500

wherein R represents an at most bicyclic aromatic radical containing atleast as many sulfonic acid groups as aromatic G-membered nuclei, saidradical being selected from the group consisting of benzene monosulfonicacid, benzene disulfonic acid, u-naphthyl disulfonic acid, andfi-naphthyl disulfonic acid radicals, X represents lower acylamino withat most 3 carbon atoms, which is bound to the benzene nucleus by itsnitrogen atom, and Y represents a member selected from the groupconsisting of hydrogen, lower alkyl and lower alkoxy.

2. A water-soluble monoazo dyestuif of the formula 6. The monoazodyestufi? which in its free acid state (@WPO'PHW1 corresponds to theformula SOQH NHCONH: R1N=N NH i fi N NHO CO1 o t i t 01 N Cl 083 0wherein n represents a whole number up to 2, X represents lower ac lwith at most 3 carbon atom and R represents sulfgphenyL S 1 7. Themonoazo dyestufl which 1n 1ts free acid state 3. A water-soluble monoazodyestutf of the formula corresponds to the formula (on-roman, 808EIIITHCOCHS N: 7 EN -NH- 2 cl-01 N N T I I II so H -GH N\ N i c C a awherein n represents a whole number up to 2, X represents lower acylwith at most 3 carbon atoms, which is cones ends to the formula bound tothe NH group by its CO- group and R p NHOOOH represents disulfonaphthyl.3

8. The monoazo dyestufi which in its free acid state X I l a H C N 01 9.The monoazo dyestufi which 1n 1ts free acid state wherein n represents awhole number up to 2, and X orresponds to the formula represents a loweracyl group of at most 3 carbon atoms. S0311 NHCOCHa 5. The monoazodyestufi which in its free acid state corresponds to the formula s 0:11NH0 0 CH;

0 References Cited in the file of this patent ('11 5o FOREIGN PATENTS760,347 Great Britain Oct. 31, 1956 UNITED STATES PATENT OFFICECERTIFICATE OF CORRECTION Patent No. 2,903,442 September 8, 1959 HenriRiat It is hereby certified that error appears in the-printedspecification of the above numbered patent requiring correction and thatthe said Letters Patent should read as oorrected below.

Column 5, lines 45 to 50', claim 5, the lower right-hand portion of theformula should appear as shown below instead of as v in the patent:

/N NII-{f |0|=- 21 N \C/ (SEAL) Signed and sealed this 17th day of May1969.

Attest:

KARL H, AXLINE ROBERT c. WATSON Attesting Officer Commissioner ofPatents

1. A WATER-SOLUBLE MONOAZO DYESTUFF OF THE FORMULA